Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C253/00—Preparation of carboxylic acid nitriles
  • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

• the present invention relates to a process for the preparation of 3-cyano-2,4-dihalogen-5-fluoro-benzoic acids, Intermediates for performing the process and methods of making these intermediates.
• 3-cyano-2,4-dichloro-5-fluoro-benzoic acid is known from DE-A-3 702 393. It will prepared from 3-amino-2,4-dichloro-5-fluoro-benzoic acid by diazotization and reaction of the diazonium salt with cyanide salts. This procedure is particularly important for Unfavorable to carry out on a larger scale.
• X and Y are preferably fluorine or chlorine. Particularly preferred they stand in the compounds of the formulas (II) and (IV) for identical radicals Fluorine or chlorine.
• the compounds of the formula (III) are particularly 2,4-dichloro-5-fluoroisophthalonitrile prefers.
• R preferably represents methyl, ethyl, propyl or benzyl.
• the hydrolysis takes place in the presence of acids and water.
• acids can organic and inorganic strong acids can be used. May be mentioned as such HCl, HBr, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, Benzenesulfonic acid, toluenesulfonic acid and strongly acidic ion exchanger in the presence of water.
• the acid used as the reagent can be used in excess or as a solvent organic solvent can be used.
• organic solvents acids such as formic acid, acetic acid, propionic acid, ethers such as dimethoxyethane, Dioxane, ketones such as acetone, butanone.
• reaction components can be combined in any order become. Then it is heated to the required temperature.
• the reaction temperature is in the range from 0 to 200 ° C, preferably 20 to 150 ° C.
• the reaction can be depressurized or under a pressure of 0 to 50 bar, preferably 0 to 6 bar.
• the products may become from the reaction mixture after dilution Filtered water. If the acid is used in large excess or a solvent, so it may be advantageous to distill off and extract the product isolate.
• the hydrolysis is carried out with acids in the presence of water.
• Organic acids and inorganic strong acids can be used. May be mentioned as such HCl, HBr, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, Toluene sulfonic acid and strongly acidic ion exchanger in the presence of Water.
• the acid used as the reagent can be used in excess or as a solvent organic solvent can be used.
• organic solvents acids such as formic acid, acetic acid, propionic acid, ethers such as dimethoxyethane, Dioxane, ketones such as acetone, butanone.
• reaction components can be added in any order. Subsequently is heated to the required temperature.
• the reaction temperature is in the range from 0 to 200 ° C, preferably 20 to 150 ° C.
• the reaction can be depressurized or under a pressure of 0 to 50 bar, preferably 0 to 6 bar.
• the products may become from the reaction mixture after dilution Filtered water. If the acid is used in large excess or a solvent, so it may be advantageous to distill off and extract the product to isolate
• esters of formula (IV) used as starting products are new. Your manufacture is described below.
• the hydrolysis takes place in the presence of acids and water.
• acids can organic and inorganic strong acids can be used. May be mentioned as such HCl, HBr, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, Benzenesulfonic acid, toluenesulfonic acid and strongly acidic ion exchanger in the presence of water.
• the acid used as the reagent can be used in excess or as a solvent organic solvent can be used.
• organic solvents come into consideration acids such as formic acid, acetic acid, propionic acid, ethers such as dimethoxyethane, Dioxane, ketones such as acetone, butanone.
• reaction components can be added in any order. Subsequently is heated to the required temperature.
• the reaction temperature is in the range from 0 to 200 ° C, preferably 20 to 150 ° C.
• the reaction can be depressurized or under a pressure of 0 to 50 bar, preferably 0 to 6 bar.
• the products may become from the reaction mixture after dilution Water extracted. If the acid is used in large excess or a solvent, it can be advantageous to distill off.
• the reaction proceeds via the imino ester and its hydrolysis Water.
• the formation of the corresponding amide is observed as a side reaction. If no water is added, amide formation becomes the main reaction (see below).
• the compound of formula (II) is prepared by hydrolysis of the corresponding one Dinitriles with acids in the presence of water and alcohols.
• reaction takes place in the presence of 1 to 10 equivalents of water and primary and secondary aliphatic alcohols.
• Methanol, ethanol, propanol are preferred and butanol.
• Organic and inorganic strong acids can be used as acids such as HCI, HBr, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, Benzenesulfonic acid, toluenesulfonic acid and strongly acidic ion exchanger.
• 1 to 10 mol of water can also be added to 1 mol of dinitrile be used.
• the reaction can be carried out with or without a solvent.
• a solvent may be the alcohol used as a reagent in excess or an inert organic Solvents are used.
• inert solvents All inert organic solvents such as hydrocarbons such as pentane, Hexane, heptane, petroleum ether, gasoline, ligroin, benzene, toluene; halogenated hydrocarbons such as dichloromethane, chloroform, chlorobenzene, dichlorobenzene, trichloroethane; Ethers such as diethyl ether, dipropyl ether, dibutyl ether, ethylene glycol dimethyl ether, Diethylene glycol diethyl ether.
• hydrocarbons such as pentane, Hexane, heptane, petroleum ether, gasoline, ligroin, benzene, toluene
• halogenated hydrocarbons such as dichloromethane, chloro
• the reaction temperature is in the range from -20 to 150 ° C. 10 to are preferred 100 ° C.
• the reaction can be carried out at normal pressure or elevated pressure from 0 to 50 bar become. 0 to 6 bar are preferred.
• the reaction mixture is diluted with water and extracted. If the alcohol in large excess or an inert solvent has been used, the solvent can be distilled off beforehand. As a by-product of the reaction Amide can be separated off.
• the reaction proceeds via the intermediately formed imino esters, from which they are split off of the alkyl radical the amides are formed.
• the reaction takes place with primary or secondary aliphatic alcohols Presence of acids.
• Methanol, ethanol, propanol and butanol are preferred. Methanol is particularly preferred.
• Organic and inorganic acids can be used strong acids are used, such as HCl, HBr.
• the reaction can be carried out with or without a solvent.
• a solvent may be the alcohol used as a reagent in excess or an inert organic Solvents are used.
• inert solvents include hydrocarbons such as pentane, Hexane, heptane, petroleum ether, gasoline, ligroin, benzene, toluene; halogenated hydrocarbons such as dichloromethane, chloroform, chlorobenzene, dichlorobenzene, trichloroethane, Ethers such as diethyl ether, dipropyl ether, dibutyl ether, ethylene glycol dimethyl ether, Diethylene glycol diethyl ether.
• hydrocarbons such as pentane, Hexane, heptane, petroleum ether, gasoline, ligroin, benzene, toluene
• halogenated hydrocarbons such as dichloromethane, chloroform, chlorobenzene,
• the reaction temperature is in the range from -20 to 150 ° C. Preferably -0 ° to 100 ° C.
• the reaction can be carried out at normal pressure or elevated pressure from 0 to 50 bar become. 0 to 6 bar are preferred.
• the products may become from the reaction mixture after dilution Filtered water. If the alcohol is in large excess or an inert solvent was used can be distilled off beforehand.
• the halogen exchange takes place by reaction with inorganic chloride salts.
• MgCl 2 and CaCl 2 can be used as inorganic chloride salts.
• the reaction can also be catalyzed by, for example, tetraalkylammonium salts, crown ethers, etc.
• the inorganic salt is used with 0.5 to 10 mol per fluorine to be exchanged. 0.5 to 2 moles are preferred.
• the reaction can be carried out with or without a solvent.
• a solvent all inert organic solvents, e.g. Pentane, hexane, Heptane, petroleum ether, gasoline, ligroin, benzene, toluene, dichloromethane, chloroform, Chlorobenzene, dichlorobenzene, trichloroethane, ethers such as dibutyl ether, ethylene glycol dimethyl ether, Diethylene glycol diethyl ether, ketones such as acetone, methyl ethyl ketone, Cyclohexanone, as well as N-methylpyrrolidinone, dimethyl sulfone, sulfolane.
• the substances are mixed and heated to the desired temperature.
• the Order of addition does not matter.
• one or two fluorine atoms are exchanged for chlorine.
• the reaction temperature is in the range from 50 to 350 ° C. 90 to are preferred 250 ° C.
• the reaction can be carried out with or without pressure. Low when used boiling solvents can be carried out under pressure favorable. Pressure range: 0 to 100 bar overpressure. Preferred: 0 to 50 bar.
• the products are isolated by filtering off the inorganic salts and that Filtrate fractionally distilled. If a water-miscible solvent was used, it can also be poured onto water and extracted.
• 3-Cyan-2,4-dihalogen-5-fluoro-benzoic acid can e.g. to manufacture the following compounds (VIII) known from US Pat. No. 4,990,517 can be used:
• the acid chloride of 3-cyano-2,4,5-trifluorobenzoic acid can be prepared from the esters of the formula (IV) according to the following scheme:
• the compounds of the formula (VIII) can be reacted with suitable ones Amines antibacterial compounds are produced.

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• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1997
  • 1997-08-01 DE DE19733243A patent/DE19733243A1/de not_active Withdrawn
• 1998
  • 1998-07-18 KR KR10-2000-7000627A patent/KR100517632B1/ko active IP Right Grant
  • 1998-07-18 UA UA2000021174A patent/UA54539C2/uk unknown
  • 1998-07-18 HU HU0002930A patent/HU224131B1/hu active IP Right Grant
  • 1998-07-18 US US09/463,272 patent/US6462218B1/en not_active Expired - Lifetime
  • 1998-07-18 BR BRPI9811579-0A patent/BR9811579B1/pt not_active IP Right Cessation
  • 1998-07-18 NZ NZ502587A patent/NZ502587A/en not_active IP Right Cessation
  • 1998-07-18 WO PCT/EP1998/004468 patent/WO1999006360A1/de active IP Right Grant
  • 1998-07-18 PT PT98943740T patent/PT1001929E/pt unknown
  • 1998-07-18 CN CN98807849A patent/CN1125042C/zh not_active Expired - Lifetime
  • 1998-07-18 RU RU2000105245/04A patent/RU2214998C2/ru active
  • 1998-07-18 JP JP2000505122A patent/JP4404476B2/ja not_active Expired - Lifetime
  • 1998-07-18 EP EP98943740A patent/EP1001929B1/de not_active Expired - Lifetime
  • 1998-07-18 PL PL338215A patent/PL191606B1/pl unknown
  • 1998-07-18 AT AT98943740T patent/ATE235461T1/de active
  • 1998-07-18 ES ES98943740T patent/ES2190602T3/es not_active Expired - Lifetime
  • 1998-07-18 DK DK98943740T patent/DK1001929T3/da active
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  • 1998-07-18 DE DE59807664T patent/DE59807664D1/de not_active Expired - Lifetime
• 2001
  • 2001-03-02 HK HK01101537A patent/HK1030598A1/xx not_active IP Right Cessation

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